Incorporation of Pertechnetate and Perrhenate into Corroded Steel Surfaces Studied by X-ray Absorption Fine Structure Spectroscopy
Batch reaction experiments and solid-phase characterization analyses were completed to examine the uptake of dissolved perrhenate [Re(VII)] or pertechnetate [Tc(VII)] by A-516 steel coupons that corroded in simulated groundwater solutions or dilute water. The goal was to identify the mechanism(s) that control the uptake of 99Tc by corrosion products on carbon steel in the presence of dilute solutions. X-ray absorption fine structure spectroscopy (XAFS) was used to study the oxidation states of Re and Tc incorporated into the corroded steel coupon surfaces. X-ray fluorescence maps showed that the corroded coupons contain localized regions enriched in Re or Tc. The Re L3 near edge XAS results for the coupons reacted with Re-spiked waters were consistent with all sorbed Re being present as perrhenate and not significantly reduced to Re(IV). Linear combination fits of the EXAFS signals for the perrhenate and ReIVO2 standards indicate that Re sorbed to the steel coupons corroded in simulated J-13 (a relatively dilute Na-HCO3-CO3 groundwater) and even more dilute waters consists of a maximum of 5 and 10% Re(IV), respectively. The fluorescence results also showed that the Re concentrations increased with increasing time of exposure to the x-ray beam time, which suggests that the perrhenate ions are only weakly bonded to the matrix of the corrosion product. In contrast to the Re results, the Tc K edge XAFS results for the coupons reacted in 99Tc-spiked waters indicate that most of the sorbed Tc had been reduced to Tc(IV). The shape of the near edge and extended fine structure is similar to the Tc(IV)-hydrous ferric oxide (HFO) and not the TcO2-nH2O standard. Differences were noted in the XAS results for steel coupons reacted with waters spiked with 0.001 versus 0.1 mmol/L 99Tc in that much more of the sorbed Tc from 0.001 mmol/L 99Tc experiments was in the form of pertechnetate. Comparison of the XAS results for coupons reacted with 0.001 mmol/L 99Tc-spiked dilute simulated Na-HCO3-CO3 groundwater versus 0.001 mmol/L 99Tc-spiked dilute water also suggest that there are likely differences in the sorption mechanism for the pertechnetate fraction in the corrosion product which formed in these two test solutions. The cause for these differences is not known, but is likely due differences in the compositions of the dilute simulated Na-HCO3-CO3 groundwater and more dilute waters, such as the dissolved carbonate concentrations.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1038353
- Report Number(s):
- PNNL-SA-73732; RAACAP; DF0961000; TRN: US201208%%444
- Journal Information:
- Radiochimica Acta, Vol. 100, Issue 4; ISSN 0033-8230
- Country of Publication:
- United States
- Language:
- English
Similar Records
Rhenium Uptake, as Analogue for Tc-99, by Steel Corrosion Products
Rhenium Uptake as Analogue for 99Tc by Steel Corrosion Products